Condensation products from the arylamids of 2.3-oxynaphthoic acid and formaldehyde and azo dyestuffs therefrom and process of making same.



N TED s'rA'rns PATENT ornion.

ARTHUR ZITSCI-IER, FELIX KUNERT, AND EDWIN ACKER, 0F OFFENBAOH-ON-THE- MAIN, GERMANY, ASSIGNORS TO THE CORPORATION OF CHEMISCHE FABRIK GRIES- HEIM-ELEKTRON, OF FRANKFORT-ON-THE-MAIN, GERMANY.

CONDENSATION PRODUCTS FROM THE ARYLAMIDS 0F 2.3-OXYNAPI-ITHOIC ACID AND FORMALDEHYDE AND AZO DYESTU'FFS THEREFROM AND PROCESS OF MAKING SAME.

1 ,122 56 L Specification of, Letters Patent.

80 Drawing.

To all whom it may concern.-

Be itknown that we, ARTHUR ZITSGHER, FE- LIx K'UNERT, and EDWIN AcKER, citizens of the German Empire, and residents of Offenbach-onfthe-Main, in the Grand Duchy of Hesse, Germany, have invented new and useful improvements in condensation products from the arylamids of 2.3-oxynaph- 'thoic acid and formaldehyde and azo dyestuffs therefrom and processes of making same, of which the following is a specification.

Our invention relates to the manufacture.

of condensation products from the axr ylamids of 2.3-oxynaphthoic acid of the general formula - hyde to act upon the arylamids of 'oxynaphthoic acid in alkalinesolut on already at ordinary temperature new compounds are formed and that these condensation products can be used for the production of azo dyestuffs by combining wlth a =non-' sulfonated diazo compound either. separately or on the vegetable fiber."

Under the term a non sulfonated diazo compound we include besides the simple non-sulfonated diazo compounds also nonsulfonated tetrazo compounds and diazo derivatives of aminoazo compounds. The constitution of the new condensation products is unknown, but they are strictly dis tinguished from the parent products and also from N-methylol derivatives like those, which Einhorn has obtained by condensing amids of acids with formaldehyde in presence of an alkali (see Annalen 1Z6? Uhemz'e,

volume 343, page 207' and the German Let ters Patent No. 157355)." Without any doubt they are typical arylamids of 2.3- oxynaphthoic acid, as it is shown byall their behavior for instance the yellowcolor Patented Dec. 29, 1914..

Application filed April 17, 1914. Serial N 0. 832,522.

of their alkaline solutions typical for arylamids, and by their reaction on diazo compounds.

- The new condensation products are, when dry, feebly colored powders relatively easily soluble in the most of the usual organic solvents, being decomposed when heated, be-

coming brown, soluble in diluted caustic soda lye to a yellow solution,

. For the production of azo dyestuffs. the

separated products, but also the solutions can be used, which are formed by mixing the solutions of the arylamids of 2.3-oxynaphthoic acid with formaldehyde. I The dyestuffs can be produced either separately or on the fiber.

The following examples will serve to illustrate further how our invention can be carried into practical effect, but it is not confined to these examples. The parts are by weight.

Example I: Into a solution of 26.3'parts of the anilid of 2.3-oxynaphthoic acid in diluted caustic soda lye, 10 parts of an aqueous solution of. formaldehyde of 30 per cent. strength are poured at ordinary temperature. After stirring for some time the product is precipitated by adding diluted hydrochloric acid, filtered, washed until neutral, pressed and dried at low temperature. It forms a feebly yellowish powder,

easily soluble in aceton, alcohol, ether,

ethyl acetate and acetic acid, more sparingly soluble in benzene, petroleum ether or solvent naphtha. When heated it is decomposed becoming brown. It is soluble in diluted caustic soda lye'to a yellow solution. Instead of the anilid of 2.3-oxynaphthoic acid its substitution products and analogues can be used. c The proportion offormaldehyde and the temperature of reaction can be varied from those given in the example.

Example II: A caustic alkaline solution-of 27.6 parts of the analid of 2.3-oxynaphthoic acid is slowly mixed while stirring with 10.5

parts of an aqueous solution of formaldehyde of 30 per cent. strength, and stirred for half'an hour at ordinary temperature: After addition of such a quantity of so. diumacetate that the solution does not containmineral acid at theendof the reaction,

the solution is poured while Stirring well into a solution, prepared in usual manner, of a diazo compound from 15.2 parts of para-nitro-ortho-toluidin on, are, :NO,=1 =2 :4

The dyestuif separates in the form of red flakes; when the combination is complete the dyestufl is filtered, washed until neutral and preferably used in form of a paste for the production of lakes. When dry it forms a bright red powder, soluble in concentrated sulfuric acid to a bluish red solution.

Example TIT: Production on cotton yarn of the dyestuff obtainable by combining diazotized paranitranilin with the condensation product from formaldehyde and the analid of 2.3-oxynaphthoic acid: The completely dried, bleached or raw cottonyarn well boiled with carbonate of soda or caustic soda, is impregnated with the following solution and completely dried: analid of 2.3-oxynaphthoic 120 grams, caustic soda lye of 35 Baum 200 ccm., formaldehyde of 30 per cent. strength 120 ccm., ricinoleate of soda of per cent. strength 200 grams-made up to 10 liters. Then it is introduced into the dyebath, well handled, wrung out and allowed to hang for a short time before being passed through the bath a second time, if necessary.

The dye-bath is prepared as follows:

Diazo s0Zuti0n.-560 grams of para-nitranilin are stirred with 500 ccm. of hot water, and 315 grams of sodium nitrite are added. The nitrite of soda being completely dissolved, this paste is poured while stirring continuously into a mixture of 4000 grams of ice, 2000 grams of ice-water and 1040 ccm. of hydrochloric acid of 20 Be...

After a short time the whole is filtered and made up to 10 liters.

Dye-batk.-5 liters of the diazo solution are mixed with 14 liters of ice-water, and shortly before dyeing 1200 ccm. of a solution of sodium acetate (1 :1) are added. In this manner beautiful red tints fast to rubbing are obtained.

Example IV: Production on cops of the dyestufi, obtainable by combining tetrazotized dianisidin with the condensation product from formaldehyde and the anilid of 2.3-oxynaphthoic acid: The cops are impregnated in the Obermaier apparatus with the following solution, then thoroughly drained and well dried: 120 grams of anilid of 2.3-oxynaphthoio acid, 200 grams of caustic soda lye of 35 Baum, 120 com. of an aqueous solution of formaldehyde of 30 per cent. strength, 200 grams of ricinoleate of soda of 60 per cent. strength-made up to 10 liters.

The diazo solution is prepared as follows:

240 grams of dianisidin arestirredwith 210 meanestccm. of hydrochloric acid of 20 Be. and dissolved in 2500 grams of boiling water. To the cold solution are added 2000 grams of ice and 150 ccm. of hydrochloric acid of 20 Baum. and a solution of 160 grams of sodium nitrite in 500 grams of water is allowed to run in slowly while stirring continuously and the whole made up to 10 liters.

' The dye-bath is prepared as follows: 1000 ccm. of'the diazo solution are mixed with 100 com. of a solution of cupric chlorid of 40 Baum, 24 com. of a solution of chromic acid (1:10) and 200 com. of a solution of aluminium acetate of 12 Baum and shortly before dyeing 150 com. of a solution of sodium acetate (1:1) are added; the whole is made up to 20 liters. The dried material is dyed in the dye-bath, well drained once more, washed and soaped. In this manner greenish blue tints are obtained fast to rubbing, especially fast to light and excellently fast to soap and chlorin, nearly coming up to the indigo tone. Cross reels and loose cotton can be dyed in like manner.

In this process cotton goods, which have been impregnated with a solution of the condensation product from formaldehyde and an arylamid of 2.3-oxynaphthoic acid, can be treated with a diazo compound while still wet, without being dried. With other nonsulfonated diazo, diazo-azo, or tetrazo compounds the'process can be conducted in a corresponding manner. Thus the shade obtainedby combining the diazo compounds of ice-black-base, that is a mixture of dianisidin and benzidin, is dark bluishblack, of para-toluidin bright reddish orange, of pseudo-cumidin bright bluish red, of orthoanisidin a bluish red, of oz-napthylamin a darkyery bluish bordeaux.

Instead of the condensationproduct from formaldehyde and the analid of. 2.3-oxynaphthoic acid, the condensation products from formaldehyde and other arylamids of 2.3-oxynaphthoic acid may be used; for instance those from the toluidids or the chloro or nitranilids. Thus, by combining the diazo compound of meta-nitro-ortho-anisidin with the condensation product from formaldehyde and the meta-nitranilid of 2.3

by Letters Patent is the following:

1. The process of making azo dyestuffs consisting in causing formaldehyde to act upon the arylamids of 2.3-oxynaphthoic acid in presence of an alkali and in combining the vention, we have signed our names in prescondensation products thus obtained with a ence of witnesses,this 30th day of March non-sulfonated diazo compound. 1914. I

2. As new articles the condensation products from the arlyamids of 2.3-oxynaphthoic acid and formaldehyde, which are, when dry, feebly colored powders, relatively easily soluble in the most of the usual organic solvents, being decomposed, when heated,- becoming brown, soluble in diluted caustic soda lye to a yellow solution.

That we 'claim the foregoing as our in-' ARTHUR ZITSCHER. FELIX KUNERT. EDWIN AOKER. Witnesses as to Arthur Zitscher and Felix Kunert: JEAN GRUND, CARL GRUND. Witnesses as to Edwin Acker: CLARENCE CORRIGAN, MARIUS HERMAZ. 

